This invention relates to a process for the production of polyester resinous products by chemically reacting an organic epoxide compound, an oxidated silicon compound and a polycarboxylic acid and/or a polycarboxylic acid anhydride.
The polyester resinous products may be utilized as a protective coating for wood, metal, plastic, linoleum, leather, fabric and rubber. They may be utilized in paints, lacquers, metal primers, caulking compounds and water-emulsion paints. The unsaturated polyester silicate resinous products, when copolymerized with a polymerizable organic compound, will produce hard, solid, useful objects or they may be used in conjunction with a reinforcing filler such as fiberglas fibers or cloth, paper, wire mesh, etc., to produce a laminate of outstanding strength and durability. They may also be used as a molding powder, as an adhesive and as impregnants. These resinous products may be further reacted with epihalohydrins and polyisocyanate compounds to produce resinous products and foam.
Polyester silicate resinous products may be modified with vegetable oils, vinyl monomers, aminoplasts, phenoplasts, phenol, melamine, silicone resins, silicone silicate resins, cellulose nitrate, cellulose, polyisocyanates, cyclopentadienes, terpenes, mono-basic acids, e.g., benzoic acid and p-tertbutyl benzoic acid; they may be modified with natural resins, ethyl cellulose, chlorinated rubber, aldehyde phenol silicate resins, aldehydes, polyhydroxy compounds and other synthetic and modified natural resins. An excess of hydrated silica may be used to modify the polyester silicate resinous products by making the resin more solvent-resistant and improving its physical strength.
Polyester silicate resinous products may be produced by reacting the following components:
(a) an oxidated silicon compound; PA0 (b) an organic epoxide compound; PA0 (c) a polycarboxylic acid, a polycarboxylic acid anhydride and mixtures thereof; PA0 (d) a Lewis acid. PA0 p-benzo-quinone, PA0 2,5-dichlorobenzoquinone, PA0 2,6-dichlorobenzoquinone, PA0 chloranil, PA0 naphthoquinone-(1,4), PA0 anthraquinone, PA0 2-methylanthraquinone, PA0 1,4-dimethylanthraquinone, PA0 1-chloroanthraquinone, PA0 anthraquinone-2-carboxylic acid, PA0 1,5-dichloroanthraquinone, PA0 1-chloro-4-nitroanthraquinone, PA0 phenanthrene-quinone, PA0 acenaphenequinone, PA0 pyranthrenequinone, PA0 chrysenequinone, PA0 thio-naphthene-quinone, PA0 anthraquinone-1,8-disulfonic acid and anthraquinone-2-aldehyde; PA0 bromal, PA0 4-nitrobenzaldehyde, PA0 2,6-dichlorobenzaldehyde-2, PA0 ethoxy-1-naphthalidehyde, PA0 anthracene-9-aldehyde, PA0 pyrene-3-aldehyde, PA0 oxindole-3-aldehyde, PA0 pyridine-2,6-dialdehyde, PA0 biphenyl-4-aldehyde; PA0 4-chloro-2-nitrobenzene-phosphonic acid nitrophenols, such as 4-nitrophenol, PA0 picric acid; PA0 acetic-anhydride, PA0 succinic anhydride, PA0 maleic anhydride, PA0 phthalic anhydride, PA0 tetrachlorophthalic anhydride, PA0 perylene-3,4,9,10-tetracarboxylic acid and PA0 chrysene-2,3-8,9-tetracarboxylic anhydride, PA0 di-bromo maleic acid anhydride; PA0 aluminum chloride, PA0 zinc chloride, PA0 ferric chloride, PA0 tin tetrachloride, PA0 (stannic chloride), PA0 arsenic trichloride, PA0 stannous chloride, PA0 antimony pentachloride, PA0 magnesium chloride, PA0 magnesium bromide, PA0 calcium bromide, PA0 calcium iodide, PA0 strontium bromide, PA0 chromic bromide, PA0 manganous chloride, PA0 cobaltous chloride, PA0 cobaltic chloride, PA0 cupric bromide, PA0 ceric chloride, PA0 thorium chloride, PA0 arsenic tri-iodide; PA0 boron trifluoride, PA0 boron trichloride; PA0 acetophenone, PA0 benzophenone, PA0 2-acetylnaphthalene, PA0 benzil, PA0 benzoin, PA0 5-benzoylacenaphthene, PA0 biacene-dione, PA0 9-acetyl-anthracene, PA0 9-benzoyl-anthracene, PA0 4-(4-dimethyl-amino-cinnamoyl)-1-acetylbenzene, PA0 acetoacetic acid anilide, PA0 indandione-(1,3), PA0 (1,3-diketohydrindene), PA0 acenaphthene quinone-dichloride, PA0 anisil, PA0 2,2-puridil and PA0 furil. PA0 the hydrogen halides, PA0 sulphuric acid and PA0 phosphoric acid; PA0 acetic acid and the substitution products thereof, PA0 monochloro-acetic acid, PA0 dichloroacetic acid, PA0 trichloroacetic acid, PA0 phenylacetic acid, PA0 7-methylcoumarinylacetic acid (4), PA0 maleic acid, PA0 cinnamic acid, PA0 benzoic acid, PA0 1-(4-diethyl-amino-benzoyl)-benzene-2-carboxylic acid, PA0 phthalic acid, PA0 and tetra-chlorophthalic acid, PA0 alpha-beta-dibromo-beta-formyl-acrylic acid (mucobromic acid), PA0 dibromo-maleic acid, PA0 2-bromo-benzoic acid, PA0 gallic acid, PA0 3-nitro-2-hydroxy-1-benzoic acid, PA0 2-nitro phenoxy-acetic acid, PA0 2-nitro-benzoic acid, PA0 3-nitro-benzoic acid, PA0 4-nitro-benzoic acid, PA0 2-chloro-4-nitro-1-benzoic acid, PA0 3-nitro-4-methoxy-benzoic acid, PA0 4-nitro-1-methyl-benzoic acid, PA0 2-chloro-5-nitro-1-benzoic acid, PA0 3-chloro-6-nitro-1-benzoic acid, PA0 4-chloro-3-nitro-1-benzoic acid, PA0 5-chloro-3-nitro-2-hydroxybenzoic acid, PA0 4-chloro-1-hydroxy-benzoic acid, PA0 2,4-dinitro-1-benzoic acid, PA0 2-bromo-5-nitro benzoic acid, PA0 4-chlorophenyl-acetic acid, PA0 2-chloro-cinnamic acid, PA0 2-cyana-cinnamic acid, PA0 2,4-dichlorobenzoic acid, PA0 3,5-dinitro-benzoic acid, PA0 3,5-nitro-salycylic acid, PA0 malonic acid, PA0 mucic acid, PA0 acetosalycylic acid, PA0 benzilic acid, PA0 butane-tetra-carboxylic acid, PA0 citric acid, PA0 cyano-acetic acid, PA0 cyclo-hexane-dicarboxylic acid, PA0 cyclo-hexane-carboxylic acid, PA0 1,10-dichlorostearic acid, PA0 fumaric acid, PA0 itaconic acid, PA0 levulinic acid, PA0 (levulic acid), PA0 malic acid, PA0 succinic acid, PA0 alpha-bromo stearic acid, PA0 citraconic acid, PA0 dibromo-succinic acid, PA0 pyrene-2,3,7,8-tetra-carboxylic acid, PA0 tartaric acid; PA0 4-toluene sulphonic acid, and PA0 benzene sulphonic acid, PA0 2,4-dinitro-1-methyl-benzene-6-sulphonic acid, PA0 2,6-dinitro-1-hydroxy-benzene-4-sulphonic acid, PA0 2-nitro-1-hydroxy-benzene-4-sulphonic acid, PA0 4-nitro-1-hydroxy-2-benzene-sulphonic acid, PA0 3-nitro-2-methyl-1-hydroxy-benzene-5-sulphonic acid, PA0 6-nitro-4-methyl-1-hydroxy-benzene-2-sulphonic acid, PA0 4-chloro-1-hydroxy-benzene-3-sulphonic acid, PA0 2-chloro-3-nitro-1-methyl-benzene-5-sulphonic acid and PA0 2-chloro-1-methyl-benzene-4-sulphonic acid. PA0 1-cyclohexylamine-3-aminopropane; PA0 1,4-diaminocyclohexane; PA0 1,3-diaminocyclopentane; PA0 di(aminocyclohexyl) methane; PA0 di(aminocyclohexyl) sulfone; PA0 1,3-di(aminocyclohexyl) propane; PA0 2,4-diaminocyclohexane; PA0 N,N'-diethyl-1,4-diaminocyclohexane, and the like. PA0 N-(3-butylthio-2-hydroxypropyl) triethylenetriamine, PA0 N-(4-phenylthio-3-hydrobutyl) pentamethylenetetramine, PA0 N-(4-cyclohexylthio-3-hydrobutyl) ethylenediamine, PA0 N-(4-cyclohexylthio-3-hydrobutyl) ethylenediamine, PA0 N-(3-cyclohexylthio-2-hydropropyl) hexamethylenediamine, PA0 N-(3-diphenylphosphino-2-hydroxypropyl) triethylenetetramine, PA0 N-(3-dicyclohelylphosphino-2-hydroxypropyl) pentamethylenetetramine, PA0 N-(3-dididecylphosphino-2-hydroxylhexyl) diethylenetriamine, and PA0 N-(3-allylthio-2-hydroxypropyl) hexamethylenediamine. PA0 tolylene diisocyanate, PA0 p,p'-diphenylmethane diisocyanate, PA0 phenylene diisocyanate, PA0 m-xylylene diisocyanate, PA0 chlorophenylene diisocyanate, PA0 benzidene diisocyanate, PA0 naphthylene diisocyanate, PA0 decamethylene diisocyanate, PA0 hexamethylene diisocyanate, PA0 pentamethylene diisocyanate, PA0 tetramethylene diisocyanate, PA0 thiodipropyl diisocyanate, PA0 propylene diisocyanate, and PA0 ethylene diisocyanate. PA0 (a) 1 to 95 parts by weight of a polyester silicate resinous product, preferably with free hydroxyl group and produced by the process of this invention. PA0 (b) 50 parts by weight of polyisocyanate, polyisocyanate or isocyanate-terminated polyurethane prepolymer; PA0 (c) up to 20% by weight of a foam stabilizer; PA0 (d) up to 50% by weight of a chemically inert blowing agent, boiling within the range of from -25.degree. C. to 80.degree. C.; PA0 (e) up to 10% by weight of an activator; PA0 (f) up to 200 parts by weight of a water-binding agent; PA0 (g) up to 95 parts by weight of a polyol; PA0 (h) up to 5% by weight of an emulsifier; PA0 (i) up to 50% by weight of a curing agent.